Alkylation process



vJuly 30, 146 w, N, AXE' 2,404,897

Y v ALKYLATIO'N PRocEss Filed Nov.' 24, 41942 ATTORNEYS Patented July 30, 1946 :ALKYLATION PROCESS William Nelson Axe, Bartlesville, Okla., assignor tto Phillips Petroleum Company, a corporation Application November 24, 1942,2Serial No.466,7.62

This invention relates to the synthesis of high octane-number isoparanlnic hydrocarbons from lower molecular weight isoparains andethylene. More specifically, thisinvention Vrelates .tothe alkylation of low-boilingisoparafns with ethylenequnder moderate conditions of temperature and pressure in` the presence of -a novel alkylation catalyst. Inone specific modicationthis invention relates to an improvedprocess ,for the utilization of ethylene-in the falkylationof isoparafns suc-has isobutane to,;produceisoparan^in fractions of :exceptional V-value as :component-s of 4,aviation fuel.

The `introduction of lalkyl groups 'into the benzene .ring in the `presence fof the @various Friedel- Crafts `type catalysts is'aclassicreaction'in organic chemistry. More recently alkylation, involvingisoparaftinsand olens, has been extended tothe eld of aliphatiochemistry as a 4result of the demands for saturated hydrocarbon stocks of high octanerating in" thema-nui actureof: aviation gasoline. Even `more recently :recognition of the importance of tthefso-.called rich-mixture rating of aviation fuelszhasagiven addedlimpetus to the Asynthesis of specific hydrocarbon types. Thus itihas been` foundthat .certain gasolinas of requisite octane-rating .are deficient `in performance `*under conditions involvingthe high ',fuelair ratios often demanded yin rmilitary air-'craft operation. -Alkylated Aaromatic v*hydrocarbons have Ybeen found `to `improve the rich-mixture characteristics of high-octane gasoline, `but tbecause of their low volatilitythequantity o'fsuch additives that can'be incorporated `into theblend is necessarily limited. On the `other hand, the isoparafn, 2,3rdimethylbutane ihereinafter :referred toas `di-isopropyl, lis Ucharacterized .by :its goed rich-mixture rating and a volatility permitting v(-:oncentrationsof 10 per'centland higherlin nishedgasoline blends.

`Except ifor nearly negligible -quantities 'laboriously Visolated `from natural gasoline,` li-isopropyl is obtained primarily as'aisyntheticfproduct. i The Ymost-convenient `'direct synthesis fof K hexane thydrocarbons 4invnlvesitlie alkylati'on of isobutane with ethylene. Although :the ,alkylationfof isoparains in general and isobutane in particular with oleiins of three or Vmore carbon .atoms is now a Well 4established practice, the utilization of ethylene `in reactions of .this type has Abeen extremely difficult. Thus .certain -acid catalysts such as sulfuric and phosphoricacids, Whilerelatively .quite :elective ,in alkylation reactions .in- VQlvlng .olefns of three lorlmore carbon atoms,

t have been foundinadequate whenappliedtoisoparaiiin-ethylene reactions.

,Insofar astheprior-,artis concernedaanhydrous aluminum-chloride activated -With hydrogen chloride appears 4to be .the best catalyst described as applicable `to alkylation rWith -ethylene and lits higher homologues. However, ythere are certain valid objectionsito the.useof 4this catalyst combination -among which ythere 4may `be mentioned; isomerizationof the isoparailinsy and auto destructivewalkylation `forming high boiling .products sludge materials. Thus with olens-aboveethylene in the homologous series attempts to .minimize these undesirablecharacteristics have .been madehy 'operating `airtemperatures `below .32 F. Even with .the ,less lreactive ethylene, `a lackof specificity at .room-temperature Ioperation lhas been reported lor .the allcylation of `butano with ethylenefinlthathexanes so .produced amounted .toonlya minor proportion ofthe total .alkylate andthe.difisopropylfraction made uponly. a-still smallerzpen cent .of the total alkylate.

'It is `.the `object cf` the present .invention to providea `process 'for the alkylation of isoparalns in general, vand ,isobutane in particular, .with ethylene employingan improved catalyst-,capable ofpperating with .a .lhigh degree of specificity undcroperating conditions conveniently attained in industrial practice. The specific action 'of my novel catalyst will .be illustrated '.by subsequent .data showing the .:total alkylate to have an isohexanecontent 4ranging from `50.tc 80 volume per cent With pure `di-isopropyl comprising 93 to 95 .per cent ofthe isohexane fraction. Other objectsand advantages will be apparent `from .the accompanying disclosure and discussion.

This applicationis a continuation-impart 'of my. copending application SerialNo. 459,985,.filed September 28, 1942, in Whichisbroadly disclosed the use of my preferred catalystin the alkylation of isoparaflins With olens.

The catalyst composition of this invention .is preparedby treating phosphoric acid of variable Water content with anhydrous boron fluoride until complete saturation has been realized. With per cent phosphoric acid substantially one mol of boron iiuoride is absorbed per mol of acid While in the case of aqueous solutions `both the phosphoric acid and water absorb boron iiuoride approximately mol for mol. 'No theories are advanced as to the chemistry .involved in the catalyst preparation, but it .is `presumed that a type of chemical combination often referred to as a complexer addition compound'has resulted. "The complex derived from boron fluoride and Water is usually designated as boron uoride hydrate. Where 100 per cent phosphoric acid is concerned, the empirical representation of its complex with boron uoride is HsPO4.BFs. In the same manner` catalysts prepared from aqueous phosphoric acid and boron fluoride would be a mixture of the following components: H3PO4.BF3 and HzOtBFa.

The boron fluoride-orthophosphoric acid catalyst is prepared by adding gaseous boron fluoride to the acid, or an aqueous solution thereof. The resulting reaction is exothermic and the rate of boron fluoride addition is usually controlled together with external cooling of the addition product and/or products to avoid temperatures much above 200 F. Saturation of the acid solution and completion of the preparation is denoted usually by escaping boron fluoride fumes or by a constant specific gravity.

The presence of boron fluoride hydrate in the catalyst composition is not essential to the catalysis of the isobutane-ethylene reaction although it may co-operate and/or promote the activity of the H3PO4.BF3 complex. On the other hand relatively large percentages of the hydrate do not interfere with this reaction as may be the case where alkylation of the higher molecular weight olens are concerned. Since the polymerizing activity of the hydrate is well known high percentages are to be avoided with oleflns such as the butylenes. However, with regard to ethylene alkylation a wider latitude is possible since ethylene exhibits a much greater resistance to polymerization.

The phosphoric acid employed may be in concentrated form, ranging from the 85 per cent acid of commercial grade up to about 100 per cent or more of HaPOr; or aqueous solutions containing as little as 20-40 per cent H3PO4 may be employed. For most applications the moderately concentrated to concentrated acid is ordinarily preferred for several reasons: (1) a considerable economy in boron fluoride consumption per volunie or per unit weight of catalyst is effected; (2) less boron fluoride is carried away with the eiiluent hydrocarbon; (3) the production of a less corrosive catalyst; (4) a better recovery of boron uoride from spent catalyst by convenient means.

The unique action of aqueous phosphoric acid in the preparation of my preferred catalyst is demonstrated by the fact that other mineral acids such as'sulfuric acid and hydrochloric acid fail to result in catalysts of comparable activity even though the quantity of boron fluoride hydrate may be appreciable. This is especially true of sulfuric acid which appears to have an inhibiting effect on the catalytic activity of boron fluoride complex compounds.

I have discovered that the alkylation of isobutane with ethylene to produce a high yield of di-isopropyl is smoothly and eciently promoted by catalysts which comprise saturated solutions of boron fluoride in ortho phosphoric acid of variable Water content. While the alkylation process can be carried out under a Wide range of mild conditions it often comprises the contacting of controlled molar proportions of isobutane and ethylene with the liquid catalyst under conditions that produce a high degree or even sub1 stantially complete ethylene utilization. The hydrocarbon product mixture is continuously separated from the catalyst and the alkylate is separated from unconverted isobutane by means of fractional distillation. Subsequent distillation is employed to separate the di-isopropyl from the 4 total alkylate. Alternately, if desired, the alkylate may be fractionated to separate traces of high boiling material and employed directly as a blending agent in the preparation of high octane aviation fuels.

A specific preferred embodiment of the process is illustrated in the fiow'diagram which shows diagrammatically an arrangement for process equipment for the continuous alkylation of isobutane With ethylene to produce and segregate products valuable as blending ingredients of aviation gasoline. Ethylene and isobutane are withdrawn fromsuitable sources, represented by storage tanks I and 2 and passed by means of pump 3 to feed tank 4. 'Ihe isobutane-ethylene blend is fed to reactor 6 by means of pump E. Reactor 6 is equipped With means of agitation such as motor driven agitators, jet mixers, a recirculation pump, or the like, and line 3@ may be used, when necessary, to drain they reactor. Provision is also made for removal of the heat of reaction by conventional design. An emulsion of hydrocarbonv and catalyst is continuously Withdrawn from the reactor to catalyst separator 'I. Becausey of the relatively high specific gravity of the catalyst, separation by gravity is rapidly effected vand a portion of the catalyst phase is drawn 01T into tank 8 and a portion is discarded through line I2 for recovery of boron fluoride. Make-up catalyst is provided by the introduction of boron fluoride from line I3 and partially saturated acid delivered from the washer I4 by line I5. Maintenance of a catalyst phase completely saturated with boron fluoride is the function of tank B. From tank 8 the catlalyst is delivered to tank 9, from which itis pumped backthrough line IU by pump. Il, 'into reactor 6. If desired, a portion'of the catalyst may be directly recycled from separator 'i through line 32.

Eiliuent hydrocarbon is passed from Vseparator 'I into washer I4 where intimate contacting with phosphoric acid, introduced through line i5, re-

moves the last traces of boron fluoride. The acid in the Washer also serves as the feed for the prepr aration of fresh catalyst. An auxiliary Water washer or a clay tower, not shown, may be em ployed immediately following the acid Wash to remove any entrained acid. The hydrocarbon stream then is passed through line I'I into esta bilizer I8 where the isobutane is taken overhead and returned to storage via line I9. Any uncondensed gases such as ethylene or ethane, etc., may be separated and vented either from the stabilizer through line/39 or from auxiliary gas stripping equipment (not shown). The stabilized total alkylate is passed through line 26 into the fractionating column 2| where a Vpentane fraction is removed as an overhead fraction and passed to storage throughline 22. The kettle product, now comprising hexanes and heavier, is charged to fractionator 24 through line 23 and isohexanes, of which di-sopropyl is the major component, are taken overhead leaving heptane and heavier as the kettle product to be charged to fractionator 2l. A naphtha fraction in the gasoline range and of good octane number and lead response constitutes` the overhead product. The small amount of heavy alkylate is Withdrawn through line 29 for utilization elsewhere.

When the illustrated lseparation and concentration of di-isopropyl is not desired, the stabilized, substantially C4.free alkylatevmay` pass through line 3.! to fractionator 21, wherein the t fascismo?, A

small amounts of heavy alkylateffmayfbefseparature and the.',pressures:desirable inzxsibseqent hydrocarbons-are"separatedfpriortoffractiona- Often USed- Regardless 0f Operating Conditions :Ltion of theja-Hyiatemane-mannereeseiibed gfineeneraLjSufeentpressureshouldbe applied Although |the cata-lystcofr-th'ls invention *'dism "Offler t0 insure 'il-qlidflehase Operation i-infthe The ifalkylate sr-p'ro'duced from ff-is'obutane wand .-perabingf conditions; fwhemisobntanerfan ethyl- 310 ethylen 'by the' iboronl-Tluoridefcatalyst composiformance- The most important variablesare; --ia'll' boiling orange'.fofiAapproximately?0821-350"F.

Contact time, temperature, isoparain-olelnra- `*after *separation of fexcess L isoloutane.` Z'Ihe ntiosantlrhydroearhonecatalyst--ratio. :Otherwar- `SI5 SIM efocztane I'Iatirie-*cif` ther-.totalgfalkyiate@may mameswhiahf'arenargelyf. dependent on the-:mode very from about 89.0 to 90.0;forhieher.Withfa tropeuationware:degreeeof'rdispersion iofneatalyst lead response Such that the addtoneohliccfiof imthhydmcmbonImpressum j rtetraethyl leadiis -sufcientto giveaailoloctane I n general it maybe said that contact times mumbel 01 hghefor ethylene conversiomust be somewhat longer-51,20 `Jractional .dist11ation` A,of ithe Etotal f alkylate thanforizhe'highergolens Wherei-the .Contact from a iiypallfrllnlfrevealsrtheifollowing-Cmt:orsresidence ftimeinatherreactor is.` short, incompostionr liplte:fconversionnof:theethyleneenrayfresult-'even f ,VOL vperscent vowthlafullyzactiveacatalystfandinvolve;either 'SODEIIMDC .6.5 loss rorlrecyclng"ofthe;ethylene. ,-Dening the225 fHeXlIleS `-fil-0 contact time as the following ratio: A IIJeJtanes 3.5 c anes Y*16.5 m iNonanesfarid heavier 112,5

@may resultlin lk'ylate "dellcient in quality bermaintainedrini-thefreactorwmay'fvaryziwidely 6:, phoric acid to give`1`00"per"c`ent phosphoric aed impending@ aheolicieney offseontactngand ',Whichll-wasuthenfsaturate'diwith anhydroushoron "tl-leratex of 'lowthroughlthei reaction zone. \-With ilu'oide. The oalkyl'ation .treaction maw-carried *reasonably '-'goo'd La'git'ati'on-anratio :of aboutfz'four r:o'1`1t-=asfa f continuonseproeess;under"z250- poun'ds '-'vblumesof hvdreoaoonper volumeeof-f'eatalyst A-fea-gerpressm'e. 'rheiliydrocarbon phasefnn the vi-isusually a'deq-u-enze,-although higherrorf-lowerfra- 57o reactor amounted to four volumes per volume iOS may be employed Withoutimlbefialmito fficatalystoan'cl tneeaverageatimerof:lcontactwas the quality of the hydrocarbon product. iadjustedrtzn35fiminutes. reaotionptemper- *Pressures' are Lacliosenin laccordance*with the :iature-washeldiat.x100-106:.F.r.thro11ghout the "'reactionweqnirements asL determined byfthefcom- @reaction The .-rfmalsstabilizedralkylatef;hadden position" f "the feed stok,` *the reactionitemper- 17 5 overall I l(boiling range rofeo to1340;\'E qfandf-fwas ethylene.

' 7 substantially completely saturated. A di-isopropyl concentrate of 92.5 ASTM octane number made up 50 per cent of the total alkylate.

Example II The preparation of dl-isopropyl was carried out by the continuous alkylation of isobutane with ethylene in the presence of a catalyst prepared by saturating 85 per cent phosphoric acid with boron iiuoride. The catalyst contained v53 per cent by weight of boron fluoride which corresponds to a mol for mol reaction between the boron fluoride and phosphoric acid and water, respectively. Substantially complete conversion of the ethylene was realized under the following The di-isopropy1 concentrate distillingjbetween 135-139 F. comprised 53 volume per cent of the total alkylate. The refractive index of this fraction (ND20, 1.3746) and the ASTM octane number (93.1) indicate a di-isopropyl content Vof more than 95 per cent.

l Example III lThe catalyst 'described in Example II was employed in this operation. The general alkylation procedure involved the liquid-phase introduction of the isobutane-ethylene feed int'o a metal reactor containing the catalyst. The reaction was carried out as a semi-continuous process "With mechanical agitation being employed in contacting the hydrocarbon feedV and catalyst. The eiiiuent from the reactor was recycledV to the reactor along with make-up Within the following limits: l Initial hydrocarbon feed:

A completely saturated total alkylate was produced having a gravity of 76.6 API. A diisopropyl concentrate distilling between 134- 140" F. and constituting 5 3 volume per cent of the total alkylate was recovered by fractionation from a still of 20 to 25 theoretical plates. The octane rating of the concentrate was found to be 92.9 ASTM.`

n Example IV The catalyst for this run was prepared by vsaturating 50 per cent phosphoric acid with boron fluoride. The absorbed boron fluoride amounted to about 2.2 parts by Weight for each part of acid.

The hydrocarbon feed was introduced continuously into the reactor containing the catalyst in a once through operation. Substantially complete conversion of ethylene was vrealized. under the following operatingconditions:

Reaction conditions were maintained A Feedcomposition: Isobutane per cent by'weight.- .f V84.15 vEthylene do 15.85 Mol ratio,` isobutane/ethylene 2.56:1 Hydrocarbon/catalyst, volume ratio in reactor 2.5: 1 Contact. time minutes..V 30 Temperature range F-- 120-130 Pressure p. s. i-- l 225 The stabilized alkylate showed an overall boiling range of 8O to 350 F. Octane-number ratings by the ASTM method with 0.0 and 1.0 cc. of tetraethyl lead were 90.0 vand 100.0, respectively.

The di-isopropyl concentrate dlstilling between 135-139 F. amounted to 50 volume per cent of the total alkylate. The octane rating of the'clear concentrate wasv 92.5 by the ASTM'nn'ethod."

Example V .Y The catalyst for this run was prepared by saturating per cent commercial phosphoric acid with boron iiuoride. The continuous operation described in the previous example was followed in this instance. The operating conditions were as follows: 1"

Feed composition: y

Isobutane per cent-by weight 92.5

Ethylene do 7.5

Mol ratio, isobutane/ethylene 6.0:1 Hydrocarbon/catalyst, volume ratio in l reactor 1 2.5:1

Contact time minutesl- 25 'Iemperature range V.F 115-120 Pressure p. s. i 200 An isoheXane fraction boiling between 13S-139 E'. amounted to 75 percent by volume ofthe total alkylate. The ASTM octane rating of the-diisopropyl concentrate was found to be 92.7.

While the foregoing disclosure and exemplary operations have served to describe Vthe invention and specic applications thereof, it will be obvious that many modiiications are possiblewithin the scope of the broad disclosure. Thus, While alkylation of isobutane has been emphasizedwith' suitable process modifications, the alkylation of isopentane may be similarly accomplished in the presence of the catalyst compositions described. In large scale commercial operations the ethylene feed to the process is preferably of relatively high purity to avoid the handling and separationkof inert material. However, a dilute ethylene stream may be utilized, with the inert impurities (usually ethane and/or propane) being separated and returned, if desired, to the facilities producing the ethylene for further conversion. The isobutane will generally be obtained from such associated operations as segregation from reiinery or natural gasoline C4 fractions, normal butane isomerization processes, and the like. The amount-of normal butane in Ithe isobutane feed to thel process may vary appreciably, and provisions Aare usually madeA to maintain suitablylow concentration thereof, even with indicated isobutane recycle. The same considerations apply to vother isoparaiiin reactants. These and other modications and adaptations 4of lthe present process will be obvious to one skilled in the art and suitable I conditions for any particular case may be readily determined by trial.

I claim: 1. A process for the alkylation of a low-boiling isoparaflin with ethylene, which comprises reacting such an isoparaffin with ethylene in an alkylation zone under alkylation conditions in the presence of an alkylation catalyst comprising an addition compound resulting from the combination of an acid of phosphorus with boron trifluoride, separating effluents of said alkylation into a catalyst phase and a hydrocarbon phase, contacting said hydrocarbon phase with a liquid acid of phosphorus to remove nonhydrocarbon impurities including boron triiluoride, removing said liquid acid of phosphorus from said hydrocarbon phase and admixing same With at least a portion of said catalyst phase, adding boron triiiuoride to the resulting mixture, passing the resultant catalytic material to said alkylation zone, and subsequently separating from the resulting puried hydrocarbon phase paraffin hydrocarbons produced in said alkylation.

2. A process for reacting isobutane with ethylene, which comprises contacting in an alkylation zone a mixture comprising said hydrocarbons, and containing a molar excess of isobutane, under alkylation conditions with a liquid catalyst comprising essentially an addition compound resulting from saturating with boron trifluoride aqueous orthophosphorio acid containing about 85 per cent by Weight of orthophosphoric acid, intimately admixing hydrocarbons effluent from said alkylation zone with aqueous orthophosphoric acid to remove minor quantities of boron trifluoride associated therewith, separating the resulting orthophosphoric acid-containing mixture from hydrocarbons so treated, adding to said mixture additional quantities of boron trifluoride to effect substantially complete saturation thereof,

and passing the resulting material to said alkylation zone as catalyst.

3. A process for reacting a low-boiling isoparan hydrocarbon with a 'low-boiling olen hydrocarbon, which comprises contacting in an a1- kylation Zone a mixture comprising such hydrocarbons, and containing a molar excess of said low-boiling isoparaflin, under alkylation conditions with a liquid catalyst comprising essentially an addition compound resulting from saturating with boron trifluoride an acid of phosphorus, intimately admixing hydrocarbons eiiluent from said alkylation zone With an acid of phosphorus to remove minor` quantities of boron trifluoride associated therewith, separating the resulting acid of phosphorus-containing mixture from said hydrocarbons and adding to said mixture additional quantities of boron trifluoride to effect substantially complete saturation thereof, and passing the resulting material to said alkylation zone as catalyst. i

4. In a process for reacting a low-boiling isoparain hydrocarbon with a low-boiling olefin hydrocarbon by contacting in an alkylation zone a mixture comprising such hydrocarbons, and containing a molar excess of said isoparain, under alkylation conditions With a liquid catalyst comprising essentially an addition compound resulting from saturating orthophosphoric acid with boron trifluoride, the improvement which comprises intimately admixing hydrocarbons eiiiuent from said alkylation zone with a liquid orthophosphoric acid to remove minor quantities of boron triuoride associated therewith, separating the resulting mixture of liquid orthophosphoric acid and removed boron trifluoride from said hydrocarbons and adding to said mixture additional quantities of boron trifluoride to effect substantially complete saturation thereof, and passing the resulting material to said alkylation zone asY at least a portion of the catalyst employed therein.

5. The process of claim 3 in which said lowboiling isoparafn is isobutane, said low-boiling olefin is ethylene, and said liquid catalyst comprises essentally an addition compound resulting from saturating with boron trifluoride aqueous orthophosphoric acid containing about per cent by weight of orthophosphoric acid.

WILLIAM NELSON AXE. 

